Cationic cassia derivatives and applications therefor

ABSTRACT

This invention relates to cationically derivatized polycalactomannans obtained from  cassia tora  and  cassia obtusifolia  and to their use in personal care, household care, and institutional care compositions.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. Ser. No. 10/874,296 filed onJun. 18, 2004, now U.S. Pat. No. 7,262,157 which issued on Aug. 28,2007, which claims priority from U.S. Provisional Application Ser. No.60/479,793 filed on Jun. 19, 2003.

TECHNICAL FIELD

This invention generally relates to polygalactomannan derivatives. Morespecifically, the invention relates to cationically derivatizedgalactomannan polymers obtained from Cassia tora and Cassia obtusifoliaand their use in personal care, health care, household, institutionaland industrial products and the like. The cationically derivatizedgalactomannan polymers can be employed as thickeners, stabilizers,emulsifiers, spreading aids and carriers for enhancing the efficacy,deposition and delivery of chemically and physiologically activeingredients. In addition, these polymers are useful for improving thepsychosensory and aesthetic properties of cosmetic formulations in whichthey are included.

BACKGROUND

Polygalactomannans are polysaccharides that are found in the endospermmaterial of seeds from leguminous plants such as Cyamopsis tetragonoloba(guar gum), Cesalpinia spinosa (tara gum), Ceratonia siliqua (locustbean gum), and other members of the Leguminosae family. Apolyglactomannan is composed of backbone of 1→4-linkedβ-D-mannopyranosyl units with recurring 1→6-linked α-D-galactosyl sidegroups branching from the number 6 carbon of a mannopyranose residue inthe backbone. The galactomannan polymers of the different Leguminosaespecies defer from one another in the frequency of the occurrence of thegalactosyl side units branching from the polymannopyranose backbone. Theaverage ratio of D-mannosyl to D-galactosyl units in thepolygalactomannan contained in guar gum is approximately 2:1,approximately 3:1 for tara gum, and approximately 4:1 for locust beangum. Another important source of polygalactomannan is Cassia tora andCassia obtusifolia (collectively known as cassia gum). The average ratioof D-mannosyl to D-galactosyl units in the polygalactomannan containedin cassia gum is approximately 5:1.

Polyglactomannan obtained from cassia gum is schematically representedin the structure below:

wherein n represents an integer from about 15 to about 35. In anotherembodiment, n represents and integer from about 20 about 30. In stillanother embodiment of the invention, the polygalactomannan of ininvention has a number average molecular weight ranging from about200,000 to about 300,000 (GPC method using a polystyrene standard)

Polygalactomannans are hydrocolloids that have a high affinity forwater. They have been widely used as suspending, thickening,emulsifying, and gelling agents in applications as diverse asfoodstuffs, coatings, personal care compositions and in oil wellfracturing fluids. Although the use of these polymers has been met withgreat success, polygalactomannans used in their natural form havesuffered some drawbacks from a water solubility standpoint. Anunsubstituted polymannose backbone is completely insoluble in water. Theattachment of galactose side units to the C-6 atom in the recurringmannose residues of the polymannose backbone increases the watersolubility of the polymer, particularly in cold water (i.e., ambienttemperature and below). The greater the galactose side unitsubstitution, the greater is the cold water solubility properties of thepolygalactomannan. Consequently, lower ratios of D-mannosyl toD-galactosyl units in the polygalactomannan leads to better cold watersolubility. For example the polygalactomannan contained in guar gum(average D-mannosyl to D-galactosyl ratio 2:1) is soluble in cold water,while the polygalactomannan obtained from cassia gum (average D-mannosylto D-galactosyl ratio of 5:1) is only sparingly soluble in cold and hotwater.

U.S. Pat. No. 4,753,659 to Bayerlein et al. discloses inter alia thatimproved cold water solubility can be imparted to cassia gum bychemically modifying the polyglactomannan. The reaction of cassia gumpolygalactomannan with selected reagents to yield C-6 substitutedderivatives is disclosed. Exemplary reaction products include C-6substituted and unsubstituted alkyl ethers, C-6 substituted phosphateesters, and C-6 substituted quaternary ammonium compounds. Discloseduses for the chemically modified cassia gum polygalactomannans includetextile printing applications, oil well drilling auxiliaries, mining andexplosive applications.

U.S. Pat. No. 5,733,854 to Chowdhary et al. discloses a chemicallymodified guar gum and a method for its preparation. According toChowdhary et al., cationically derivatized guar gum polygalactomannansproduce clear and colorless solutions upon dispersal in aqueous ororganic solvents. A disclosed application for the cationicallyderivatized guar gum includes its incorporation into detergentcompositions for human and household uses. Other disclosed uses includepersonal care and cosmetic applications. The use of cationicallyderivatized cassia gum in personal care, pharmaceutical, home care orcosmetic formulations is not discussed.

An inherent drawback with cationically derivatized guar gumpolygalactomannans is the high ratio of galactose side units containedon the polymannose backbone. For every two mannose backbone repeatingunits there is one pendant galactose side unit. The galactose side unitsshield the hydroxyl groups contained on the C-6 atom of the mannosebackbone units from access to derivation reagents. For the most part,only the C-6 hydroxyl group on the galactose side unit is accessible forfunctionalization by derivatizing agents. Consequently, the degree ofcationic group substitution on the guar gum polygalactomannan isrelatively low.

Accordingly, there exists is a need for a derivatized polygalactomannanwith a high degree of molecular substitution which is suitable for usein thickener, stabilizer, emulsifier, spreading aid and carrierapplications for enhancing the efficacy, deposition and delivery ofchemically, cosmetically and physiologically active ingredients.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Exemplary embodiments in accordance with the present invention will bedescribed. Various modifications, adaptations or variations of suchexemplary embodiments described herein may become apparent to thoseskilled in the art as such are disclosed. It will be understood that allsuch modifications, adaptations or variations that rely upon theteachings of the present invention, and through which these teachingshave advanced the art, are considered to be within the scope and spiritof the present invention.

In one aspect, embodiments of the present invention relate topolygalactomannan compositions that have been derivatized to higherdegrees of molecular substitution than prior art polygalactomannancompositions. In some embodiments of the present invention apolygalactomannan isolated from the endosperm of the seeds of Cassiatora and Cassia obtusifolia (cassia gum) is post-functionalized tocontain recurring pendant nonionic, anionic and cationic moieties. Someexemplary embodiments in accordance with the present invention relate tocationically modified cassia gum polygalactomannan. Other embodimentsrelate to molecularly substituted cassia gum polygalactomannans that aretailored for use as thickeners, stabilizers, emulsifiers, spreading aidsand carriers for enhancing the efficacy, deposition and delivery ofchemically and physiologically active ingredients. Yet other suchembodiments relate to personal care, home care, food and industrialcompositions that contain molecularly substituted cassia gumpolygalactomannans.

As used here and throughout the specification, the terms molecularlysubstituted and molecular substitution mean appending a substituentselected from nonionic, anionic, cationic, and amphoteric containingmoieties, as well as combinations thereof, to the C-6 carbon atom of thegalactose side unit and/or to the C-6 carbon atom of the mannoserepeating backbone units of the cassia gum derived polygalactomannan.Functionalization reagents containing these moieties are co-reacted withthe hydroxyl group that is bonded to the C-6 carbon atom of thegalactose and mannose residues that make up the cassia gum derivedpolygalactomannan. In other words, a hydroxyl hydrogen is replaced by amoiety derived from the functionalization reagent. In one embodiment,the hydroxyl hydrogen on the C-6 carbon atom is replaced by a moietyderived from the functionalization reagent. The reaction isschematically represented below:

In some embodiments of the invention, R independently representshydrogen, a nonionic group, an anionic group, a cationic group, and anamphoteric group, subject to the proviso that all R groups can not behydrogen at the same time. In other embodiments, R independently isselected from the formula:—AR¹wherein A is an alkylene spacer group containing 1 to 6 carbon atoms andR¹ represents a nonionic substituent, an anionic substituent, a cationicsubstituent, and an amphoteric substituent. In another embodiment thealkylene group contains 2, 3, 4, or 5 carbon atoms. The alkylene spaceris optionally mono-substituted or multi-substituted with a groupselected from C₁ to C₃ alkyl, C₁ to C₃ haloalkyl, C₁ to C₃ hydroxyalkyl,hydroxyl, halogen (bromine, chlorine, fluorine, and iodine), andcombinations thereof. An exemplary nonionic R¹ substituent is —OH.Illustrative nonionic groups defined under —AR¹ can be represented bythe formula:-alkylene-OHwherein the alkylene spacer is defined above. Representative nonionicgroups include but are not limited to hydroxymethyl, hydroxyethyl,hydroxypropyl, and hydroxybutyl.

Exemplary anionic R¹ substituents are —COOH, —SO₃H, —OP(O)(OH)(OH), and—P(O)(OH)(OH). Illustrative anionic groups defined under —AR¹ can berepresented by the formulae:-alkylene-COOH-alkylene-SO₃H-alkylene-OP(O)(OH)(OH)-alkylene-P(O)(OH)(OH)wherein the alkylene spacer is as defined previously. Representativeanionic groups include but are not limited to carboxymethyl,carboxyethyl, and carboxypropyl.

Exemplary cationic substituents under R¹ includes 1°, 2°, and 3° aminesrepresented by the radical: —N(R²)₂, and quaternary ammonium, sulfoniumand phosphonium derivatives represented by the radicals: —N(R³)₃ ⁺X⁻,—S(R³)₂ ⁺X⁻, —P(R³)₃ ⁺X⁻, wherein R² independently represents hydrogen,linear and branched C₁ to C₅ alkyl, phenyl and benzyl; R³ independentlyrepresents C₁ to C₂₄ alkyl, benzyl and phenyl; and X is any suitableanion that balances the charge on the onium cation. In one embodiment, Xis a halide anion selected from bromine, chlorine, fluorine and iodine.The alkyl, benzyl and phenyl substituents defined under R² and R³ canoptionally be mono-substituted or multi-substituted with a groupselected from C₁ to C₃ alkyl, hydroxyl, halogen (bromine, chlorine,fluorine, and iodine), and combinations thereof. Illustrative cationicgroups defined under —AR¹ can be represented by the formulae:-alkylene-N(R²)₂-alkylene-N(R³)₃ ⁺X⁻-alkylene-S(R³)₂ ⁺X⁻-alkylene-P(R³)₃ ⁺X⁻wherein alkylene, R2, R3, and X are as previously defined.Representative of cationic groups under —AR¹ are quaternary ammoniumgroups that include but are not limited to the formula:

wherein R³ is selected from methyl, decyl, dodecyl, butadecyl,cocoalkyl, dodecyl, and octadecyl, and R⁴ is selected from hydrogen andchlorine.

The amphoteric substituents can be selected from any radical or residuethat contains both a positive and negative charge. Representativeamphoteric substituents include betaine, amino acid, dipeptides,tripeptide and polypeptide residues.

Underivatized Cassia gum or flour is commercially available from Noveon,Inc. under the Diagum trademark. As discussed supra, the derivatizationof cassia gum polygalactomannan occurs at the C-6 hydroxyl group on thegalactose side unit and/or on the backbone mannose repeating units. Thesteric hindrance of the galactose side unit controls the amount ofsubstitution that can occur at the C-6 hydroxyl group inpolygalactomannans. Cassia gum polygalactomannans differ from otherpolygalactomannans in the degree of substitution at the C-6 hydroxylgroup since the structure of cassia affords more accessibility (i.e.,less steric hindrance) of the C-6 hydroxyl reactive site, resulting inhigher degrees of functional group substitution. In embodiments of theinvention wherein ionic group substitution is effected the derivatizedcassia gum polygalactomannan will have a broader range of charge densitywhen compared to the similarly derivatized prior art polygalactomannans. In some embodiments of the invention the degree of quaternary ammoniumcationic substitution can range up to 60% and above. The term “degree ofsubstitution” refers to the percentage of available C-6 hydroxyl groupsper polygalactomannan repeating unit (represented by the bracketedrepeating unit structure above) that have been modified with themodifying substituent (e.g., 3 out of the 5 available C-6 hydroxylgroups are modified). In comparison, the derivatized prior art guarpolygalactomannans exhibit a degree of substitution of only 33%.

The derivatization of the Cassia polygalactomannan C-6 hydroxyl groupcan be accomplished by methods well known to those skilled in the art.Generally speaking, the C-6 hydroxyl group can be reacted with anyfunctionalization reagent that is co-reactive therewith. For example, tofunctionalize the C-6 hydroxyl group with the nonionic, anionic,cationic and amphoteric substituents of the invention, the C-6 hydroxylgroup(s) on the Cassia gum polygalactomannan are reacted with afunctionalization reagent that contains the respective nonionic,anionic, cationic and amphoteric substituents and a functional moietythat is co-reactive with the C-6 hydroxyl group. The functionalizationreaction is conducted in an appropriate solvent and at an appropriatetemperature. The amount of functional group substitution (degree ofsubstitution) on the polygalactomannan C-6 hyroxyl atom(s) can becontrolled by adjusting the stoichiometric amount of functionalizationreagent added to the Cassia polygalactomannan. Functionalization methodsfor Cassia gum polygalactomannans are disclosed in U.S. Pat. No.4,753,659 which is incorporated herein by reference. Additional methodsof derivatizing polygalactomannans are set forth in U.S. Pat. No.5,733,854.

In an exemplary reaction Cassia gum polygalactomannan can befunctionalized with co-reactive quaternary ammonium compounds whichcontain an epoxy group or a halohydrin group. In one such embodimentCassia polygalactomannan can reacted with glycidyltrimethylammoniumchloride (75% aqueous solution) in an alkaline aqueous medium at atemperature of about 52° C. to yield the desired2-hydroxy-3-(trimethylammonium)propyl Cassia galactomannan chlorideproduct. The reaction is schematically represented below:

Chemical modification of Cassia gum leads to incorporation of nonionic,anionic, cationic, and amphoteric moieties, and combinations thereofonto the backbone. The chemical modification leads to various physicalproperties changes. For instance, derivatized cassia gums exhibit coldwater or improved cold water solubility. It is able to hydrate in coldwater and build viscosity by forming a colloidal thixotopic dispersionin cold water.

Some embodiments of the invention relate to the use of cationic cassiaderivatives as multi-functional polymer ingredients in personal care,health care, household, institutional and industrial productapplications and the like. The cationic cassia polymers can be employedas emulsifiers, spreading aids and carriers for enhancing the efficacy,deposition and delivery of chemically and physiologically activeingredients and cosmetic materials, and as a vehicle for improving thepsychosensory and aesthetic properties of a formulation in which theyare included. The term “personal care products” as used herein includes,without limitation, cosmetics, toiletries, cosmeceuticals, beauty aids,personal hygiene and cleansing products that are applied to the skin,hair, scalp, and nails of humans and animals. The term “health careproducts” as used herein includes, without limitation, pharmaceuticals,pharmacosmetics, oral care products (mouth, teeth), eye care products,ear care products and over-the-counter products and appliances, such aspatches, plasters, dressings and the like. The term also includesmedical devices that are externally applied to or into the body ofhumans and animals for ameliorating a health related or medicalcondition. The term “body” includes the keratinous (hair, nails) andnon-keratinous skin areas of the entire body (face, trunk, limbs, handsand feet), the tissues of body openings and the eyes. The term “skin”includes the scalp and mucous membranes. The term “household careproducts” as used herein includes, without limitation, products beingemployed in a household for surface protection and/or cleaning includingbiocidal cleaning products for maintaining sanitary conditions in thekitchen and bathroom and laundry products for fabric cleaning and thelike. The term “institutional and industrial products” as used hereinincludes, without limitation, products employed for protection and/orcleaning or maintaining sanitary conditions in industrial andinstitutional environments, including hospitals and health carefacilities, and the like.

In a given composition or application, the cationic cassia derivativesof this invention can, but need not, serve more than one function, suchas a thickener and conditioner, film former and carrier or depositionaid, and the like. The amount of cationic cassia derivatives that can beemployed depends upon the purpose for which they are included in theformulation and can be determined by person skilled in the formulationarts. Thus, as long as the physicochemical and functional properties areachieved, a useful amount of cationic cassia derivatives on a totalcomposition weight basis, typically can vary in the range of about 0.01%to about 25%, but is not limited thereto.

Compositions containing cationic cassia derivatives can be packaged anddispensed from containers such as jars, tubes, sprays, wipes, roll-ons,sticks and the like, without limitation. There is no limitation as tothe form of the product in which these derivatives can be incorporated,so long as the purpose for which the product is used is achieved. Forexample, personal and health care products containing cationic cassiaderivatives can be applied to the skin, hair, scalp, and nails, or tohard surfaces or laundry fabrics, without limitation in the form ofgels, sprays (liquid or foams), emulsions (creams, lotions, pastes),liquids (rinses, shampoos), bars, ointments, suppositories, and thelike.

The cationic cassia derivatives of this invention are suitable forpreparation of personal care (cosmetics, toiletries, cosmeceuticals) andtopical health are products, including, without limitation, hair careproducts (shampoos, combination shampoos, such as “two -in-one”conditioning shampoos), post-shampoo rinses, setting and stylemaintenance agents (including setting aids, such as gels and sprays,grooming aids such as pomades, conditioners, perms, relaxers, hairsmoothing products, and the like), skin care products (facial, body,hands, scalp and feet), such as creams, lotions and cleansing products,antiacne products, antiaging products (exfoliant, keratolytic,anticellulite, antiwrinkle, and the like), skin protectants (sun careproducts, such as sunscreens, sunblock, barrier creams, oils, siliconesand the like), skin color products (whiteners, lighteners, sunlesstanning accelerators and the like), hair colorants (hair dyes, haircolor rinses, highlighters, bleaches and the like), pigmented skincolorants (face and body make-ups, foundation creams, mascara, rouge,lip products, and the like) bath and shower products (body cleansers,body wash, shower gel, liquid soap, soap bars, syndet bars, conditioningliquid bath oil, bubble bath, bath powders, and the like), nail careproducts (polishes, polish removers, strengtheners, lengtheners,hardeners, cuticle removers, softness, and the like).

Toiletries and health and beauty aids containing cationic cassiaderivatives, can include, without limitation, hair-removal products(shaving creams and lotions, epilators, after-shaving skin conditioner,and the like); deodorants and antiperspirants; oral care products(mouth, teeth, gums), such as mouth wash, dentifrice, such astoothpaste, tooth powder, tooth polishes, tooth whiteners, breathfresheners, denture adhesives, and the like; facial and body hair bleachand the like. Other health and beauty aids can contain cationic cassiaderivatives, include, without limitation, sunless tanning applicationscontaining artificial tanning accelerators, such as dihydroxyacetone(DHA), tyrosine, tyrosine esters and the like: skin depigmenting,whitening and lightening, formulations containing such activeingredients as kojic acid, hydroquinone, arbutin, fruital, vegetable orplant extracts, (lemon peel extract, chamomile, green tea, papermulberry extract, and the like), ascorbyl acid derivatives ascorbylpalmitate, ascorbyl stearate, magnesium ascorbyl phosphate and thelike); foot care products, such as keratolytic corn and callousremovers, foot soaks, foot powders (medicated such as antifungalathlete's foot powder, ointments, sprays, and the like, antiperspirantpowders, or non-medicated moisture absorbent powder), liquid foot sprays(non-medicated, such as cooling, and deodorants sprays, and the like),and foot and toenail conditioners (lotions , creams, nails softeners,and the like).

Topical health and beauty aids can include cationic cassia derivativesas spreading aids and film formers include, without being limitedthereto, skin protective sprays, cream, lotion, gels, stick, powderproducts such as insect repellants, itch relief, antiseptics,disinfectants, sun blocks, sun screens, skin tightening and toning milkand lotions, wart removal compositions, and the like.

Cationic cassia derivatives are particularly useful as suspending agentsfor particulates making them suitable for dermal products containingparticulates, microabrasives, and abrasives, such as shower gels, masksand skin cleansers containing exfoliative scrub agents. Typicalparticulates include, but are not limited thereto, shell, seed, andstone granules, such as almonds, apricot (seed, kernel powder, shell),avocado, coconut, corn cob, olive, peach, rose hip seed, walnut shell,and the like, aluminum silicate, jojoba (wax, seed powder), oyster shellpowder, evening primrose seed, milled adzuki beans, and the like,polyethylene (granules, spheres), polyethylene (and) hydroxycellulosegranules, microcrystalline cellulose, polystyrene, polystyrene (and)talc granules, ground pumice, ground loofah, ground seaweed, rice, oatbran, silica (hydrated, colloidal, and the like), ground eggshell,ground blue poppy seed, salt, such as sodium chloride, dead sea salt,and the like, and mixtures thereof.

Cationic cassia derivatives are useful as thickeners and film formers ina variety of dermatological, cosmeceutical compositions employed fortopically ameliorating skin conditions caused by aging, drying,photodamage, acne, and the like, containing conditioners, moisturizers,antioxidants, exfoliants, keratolytic agents, vitamins, and the like.Cationic cassia derivatives can be employed as a thickener for activeskin treatment lotions and creams, containing as such activeingredients, acidic anti-aging agents, anti-cellulite, and anti-acneagents, such as alpha-hydroxy acid (AHA), beta-hydroxy acid (BHA), alphaamino-acid, alpha-keto acids (AKAs), and mixtures thereof. In suchcosmeceuticals, AHAs can include, but are not limited to, lactic acid,glycolic acid, fruit acids, such as malic acid, citric acid, tartaricacid, extracts of natural compounds containing AHA, such as appleextract, apricot extract, and the like, honey extract, 2-hydroxyoctanoicacid, glyceric acid (dihydroxypropionic acid), tartronic acid(hydroxypropanedioic acid), gluconic acid, mandelic acid, benzilic acid,azelaic acid, acetic acid, alpha-lopioc acid, salicylic acid, AHA saltsand derivatives, such as arginine glycolate, ammonium lactate, sodiumlactate, alpha-hydroxybutyric acid, alpha-hydroxyisobutyric acid,alpha-hydroxyisocaproic acid, alpha-hydroxyisovaleric acid, atrolacticacid, and the like. BHAs can include, but are not limited to, 3-hydroxypropanoic acid, beta-hydroxybutyric acid, beta-phenyl lactic acid,beta-phenylpyruvic acid, and the like. Alpha-amino acids include,without being limited to, alpha-amino dicarboxylic acids, such asaspartic acid, glutamic acid, and mixtures thereof, sometimes employedin combination with fruit acids. AKAs include pyruvic acid. In someantiaging compositions, the acidic active agent may be retinoic acid, ahalocarboxylic acid, such as trichloroacetic acid, an acidicantioxidant, such as ascorbic acid (vitamin C), a mineral acid, phyticacid, lysophosphatidic acid, and the like. Some antiacne agents, forexample, can include salicylic acid, derivatives of salicylic acid, suchas 5-octanoylsalicylic acid, retinoic acid and its derivatives.

Other health care products in which cationic cassia derivatives can beincluded are medical products, such as topical and non-topicalpharmaceuticals and devices. In the formulation of pharmaceuticals, acationic cassia derivatives can be used as a thickener and/or lubricantin such products as creams, pomades, gels, pastes, ointments, tablets,gel capsules, purgative fluids (enemas, emetics, colonics, and thelike), suppositories, anti-fungal foams, eye products (ophthalmicproducts such as eyedrops, artificial tears, glaucoma drug deliverydrops, contact lens cleaner, and the like), ear products (wax softeners,wax removers, otitis drug delivery drops, and the like), nasal products(drops, ointments, sprays, and the like), wound care (liquid bandages,wound dressings, antibiotic creams, ointments and the like), withoutlimitation thereto.

The cationic cassia derivatives can be used in home care, institutionaland industrial applications (I&I), as a rheology modifier, fabricconditioning agent, especially to improve efficiency through “cling-onsurface” or improving efficacy of disinfectants, and biocidalformulations, and to synergistically improve fabric softening efficacyin combination with traditional fabric softeners. Typical household andI&I products that may contain cationic cassia derivatives, include,without limitation, laundry and fabric care products, such asdetergents, fabric softeners (liquid or sheet), ironing sprays, drycleaning aids, anti-wrinkle sprays, spot removers and the like; hardsurface cleaners for the kitchen and bathroom and utilities andappliances employed or located herein, such as toilet bowl gel, tub andshower cleaners, hard water deposit removers, floor and tile cleansers,wall cleansers, floor and chrome fixture polishes, alkali-strippablevinyl floor cleaners, marble and ceramic cleaners, air freshener gels,liquid cleansers for dishes, and the like; disinfectant cleaners, suchas toilet bowl and bidet cleaners, disinfectant hand soap, roomdeodorizers, and the like.

The cationic cassia derivatives can be used as rheology modifiers,dispersants, stabilizers, promoters, and the like, in industrial productapplications, such as, without limitation, textiles processing,finishing, printing, and dyeing aids, protective washable surfacecoatings, manufacture of synthetic leather by saturation of non-wovenfabrics, and the like, of woven or non-woven fabrics and natural orsynthetic fibers); water treatment (waste water, cooling water, potablewater purification, and the like): chemical spills containment(acid-spill absorbent, and the like); leather and hides (processingaids, finishing, embossing and the like); paper and papermaking (surfacecoating, such as pigmented coatings, antistatic coatings and the like,pulp binders, surface sizing, dry and wet strength enhancers,manufacture of synthetic fibers, such as non-woven fabrics, wet-laidfelts, and the like): printing (inks, antiwicking ink-jet printer inks,thickeners for ink formulations containing cationic dyes for printingacrylic fabrics, and the like); paints (pigments and grinding additives,crosslinking agents for epoxy latex emulsions, particulate-suspendingaids for clays, pigments and the like); industrial plant effluenttreatment (flocculants for phenolics in paper mill effluent, and thelike); metal working (acid etch cleaners, low pH metal coatings,pickling agents in cold rolled steel processing, and the like); woodpreservation: and industrial construction products for buildings androads (cement plasticizers, asphalt emulsions stabilizers at low pH,acid etch for cement, consistency modifiers of concrete, mortar, puttyand the like). The cationic cassia derivatives are also useful asthickeners for rust removers, acid truck cleaners, scale removers, andthe like, and as dispersion stabilizers of products containingparticulates, such as clay, pigments (titanium dioxide, calciumcarbonate, and other minerals), abrasives, and the like, employed in avariety of foregoing industrial applications and in drilling muds andoil well fracturing fluids.

The foregoing products typically contain various conventional additivesand adjuvants known in the art, some of which can serve more than onefunction. The amounts employed will vary with the purpose and characterof the product and can be readily determined by one skilled in theformulation arts and from the literature

It is known that formulated compositions for personal care and topical,dermatological, health care, which are applied to the skin and mucousmembranes for cleansing or soothing, are compounded with many of thesame or similar physiologically tolerable ingredients and formulated inthe same or similar product forms, differing primarily in the puritygrade of ingredients selected, by the presence of medicaments orpharmaceutically accepted compounds, and by the controlled conditionsunder which products may be manufactured. Likewise, many of theingredients employed in the products for household and I&I are same orsimilar to the foregoing, differing primarily in the amounts andmaterial grades employed. It is also known that the selection andpermitted amount of ingredients also may subject to governmentalregulations, on a national, regional, local, and international level.Thus, discussions herein of various useful ingredients for personal careand health care products may apply to household and I&I products andindustrial applications.

The choice and amount of ingredients in formulated compositionscontaining cationic cassia derivatives polymer will vary depending onthe product and its function, as is well known to those skilled in theart. Formulation ingredients for personal care and topical health careproducts can typically include, but are not limited to, solvents,surfactants (as cleansing agents, emulsifying agents, foam boosters,hydrotropes, solubilizing agents, and suspending agents), non-surfactantsuspending agents, emulsifiers, skin conditioning agents (emollients,moisturizers, and the like), hair conditioning agents (includingsilicones and silicone oils), hair fixatives, film-formers, skinprotectants, binders, chelating agents, antimicrobial agents, antifungalagents, antidandruff agents, abrasives, adhesives, absorbents,colorants, deodorants agents, antiperspirant agents, humectants,opacifying and pearlescing agents, antioxidants, preservatives,propellants, spreading agents, sunscreen agents, sunless skin tanningaccelerators, ultraviolet light absorbers, pH adjusting agents,botanicals, hair colorants, oxidizing agents, reducing agents, skinbleaching agents, pigments, physiologically active agents,anti-inflammatory agents, topical anesthetics, fragrance and fragrancesolubilizers, and the like, in addition to ingredients previouslydescribed that may not appear herein. Oral care products, for instance,can contain anti-caries, anti-tartar and/or anti-plaque agents inaddition to surfactants, abrasives, humectants, fillers, and flavorants.An extensive listing of substances and their conventional functions andproduct categories appears in the CFTA Dictionary, generally, and in Vol2, section 4 and 5, in particular.

Due its water swelling properties, cationic cassia derivatives are oftenused as a gelling agent for water-based systems. For instance, cationiccassia derivatives can be used as gelling agents for air treatment gelsthat are designed to release continuously volatile air treatment agentsfrom the gel. The volatile air treatment components can include airfreshening ingredients such as disinfectants, bactericides,insecticides, fungicides, deodorants, pest repellants, odoriferousmaterials and mixtures thereof. Odoriferous materials include oil ofrose, oil of lime, oil of lemon, oil of spearmint, oil of wintergreen,oil of cedar wood, oil of fir Canadian and the like. These oils may beused in combination with fragrances such as aromatic esters, aldehydes,ketones, and other compounds known to those skilled in the art ofblending fragrances. The level of the gelling agent ranges from about0.5 to about 25 wt. % in one embodiment, from about 0.75 to about 15 wt.% in another embodiment, and from about 1 to 5 wt. % in a furtherembodiment, wherein the weight percents are based on the total weight ofthe composition.

Cationic cassia derivatives can also be used to form hydrocolloid gelsfor wound dressing and medical devices. The healing of wounds such aswounds resulting from injury, surgery etc. is greatly dependent upon thedressing used. Conventional bandages often do not provide optimumresults. Special pressure relieving or reducing measures should also betaken. A moist dressing is also often beneficial, providing rehydrationof dehydrated tissue, increased angiogenesis (proliferation of new bloodvessels), minimal bacterial growth, physical protection, and themaintenance of the proper pH for stimulating the release of oxygen andfor allowing proteolytic enzymes to work more efficiently.

Pourable water based natural or synthetic water-soluble or waterswellable gel forming hydrocolloidal gels can be used for wounddressing. They are initially sufficiently fluid to be poured or spreadonto the wound, but, which after application can form a moist solidelastic protective gel that remains in the polymeric hydrocolloidhydrated state.

Medical devices adapted for implanting into the body to facilitate theflow of bodily fluids, to serve as vascular grafts or for other purposeshave been developed. Typically, these devices include stents, catheters,or cannulas, plugs, constrictors, tissue or biological encapsulants andthe like. Many of these devices that are used as implants are made fromdurable, non-degradable plastic materials such as polyurethanes,polyacrylates, and silicone polymers, and the like. In some instancesthey are made from biodegradable polymers, which remain stable in-vivofor a period of time, but eventually biodegrade into small moleculesthat are easily excreted form the body. Cross-linked hydrogels made fromthe cationic modified Cassia gum polygalactomannans are contemplated foruse for such medical devices. They offer excellent biocompatibility andhave been shown to reduce tendency for inducing thrombosis, encrustationand inflammation. In these applications, the hydrocolloidal polymericgel that is used for wound healing or implants, is the cationic cassiaderivative. The cationic cassia-containing compositions, mixed withwater, will form a solid temperature irreversible elastic gel, i.e.flexible gel, with or without crosslinking agents, to assist in theformation of a non-fluid system. Typical gels contain from 3 to 15 wt %cationic cassia derivatives. A greater amount of polymer andcrosslinking agents will provide a more solid gel, or a gel that willdisplay better physical and mechanical properties (modulus, stress atyield, strength). Sufficient water should be present to provide theinitial fluidity required for pouring or spreading the gel onto thewound, or inserting the gel in the body through an endoscope, in thecase of implants. Ionic and non-ionic cross-linkers are used then tosolidify the gel, and control the crosslinking density (i.e., the finalmechanical and physical properties of the gel). For most applications,the crosslinking agents are present from 0 to 8 wt %, more preferablyfrom 0.1 to 5 wt %. Any suitable non-toxic crosslinker can be used,including galactose, mannose, oligosaccharides containing either or bothmannose and galactose, borax, organic titanate, boric acid, diepoxides,polycarboxylic acids, glutaraldehyde, dihydroxyaluminum, sodiumcarbonate, citric acid, and a soluble source of any of the cations ofcalcium, magnesium and aluminum. In the case of implants, the ioniccrosslinks can be easily and selectively displaced in-vivo afterimplantation of the implant device in the body, resulting in a swellingand softening of the device in the body which enhances patient comfort.The device will retain its original configuration withoutdisintegration. If desired, any of the following substances can beincluded in the composition: medication and disinfectants, wound healingenhancers such as vitamins, blood coagulants, antibiotics, source ofoxygen etc.

Cationic polymers are often used as conditioners in skin and/or haircompositions. Quaternized polymers are used in shampoos and conditionersto facilitate compatibility. The positively charged nitrogen bonds withnegatively charged hair fibers to form films. They also make the hairfeel softer and smoother to the touch without creating too muchbuild-up. Cationic cassia derivatives can be used as part of a cationicpolymer conditioner package in a conditioning detergent formulation thatnot only imparts cleansing, wet detangling, dry detangling andmanageability properties to the hair, but also is relativelynon-irritating. This composition is thus suitable for use by youngchildren and adults having sensitive skin and eyes.

In skin care formulations, cationic cassia derivatives can be used aspolymeric skin feel and skin mildness aids in ultra-mild skin cleansingcompositions or moisturizing compositions. Cationic cassia derivativesprovide skin conditioning, skin mildness and moisturizing, whilemaintaining desirable lathering properties. Cationic cassia derivativesalso display a desirable silky, soft smooth in-use feeling, by avoidingless skin irritation though excessive defatting or over drying the skinafter multiple usage. The positively charged cationic cassia derivativescan bind with negatively charged sites on the skin to provide a softskin feel after use. It improves the sensory feel on skin by reducingtackiness and greasiness and improving smoothness.

Cationic cassia derivatives of this invention can be employed as arheology modifier or emulsion stabilizing agents in emulsions. Thecationic cassia derivatives of this invention provide better emulsionstability to foaming emulsion compositions. The need for a skincleansing composition having good dermatological compatibility isgrowing. In particular, the use of an alkyl oligoglycoside as anon-ionic surfactant has found favor due to its favorable foaming andcleaning properties, biodegradability and dermatological compatibility.However, such alkyl oligoglycosides-containing emulsions lack cosmeticappeal. These compositions are not readily absorbed by the skin andinstead of forming a creamy microfoam upon application to the skin, theyonly form a coarse macrofoam. Formulations containing cationic polymerssuch as cationic cassia derivatives lead to the formation of a rich andcreamy microfoam that is readily absorbed by the skin with high cleaningand refatting properties.

Cleansing compositions that show good conditioning and latheringproperties are highly desirable. This is difficult to achieve due to theinherent incompatibility between anionic surfactants (that show superiorcleansing with high lathering compared to other surfactants) and thecationic polymers (that provides conditioning properties and/or aids inthe deposition of therapeutic agents to the skin or hair). The presenceof such anionic surfactants in the cleansing composition also interfereswith the deposition of therapeutic agents because such compositions aredesigned to remove oil, grease and dirt and particulate matter from thehair, scalp and skin during rinsing. In personal care applications, thecationic cassia derivatives of the invention can be used along withsurfactant, water-soluble agents (for instance silicones) to provide anenhanced delivery system for therapeutic agents, conditioners,moisturizers etc. Examples of therapeutic agents include, but are notlimited to, detangling/wet combing agent, humectants, anti-acne agents,anti hair loss agents, hair-growth inhibitor agents, herbal extractsetc.

Various water-insoluble particulates (solid or liquid particles of oilemulsions) have been incorporated in detergent compositions for thepurpose of imparting desirable residual properties on surfaces washedwith such products. For instance, shampoo compositions containingparticulate antidandruff agents can not function unless such agents aredeposited and retained on the hair and scalp subsequent to rinsing.Particulate antimicrobial agents have also been used in various laundrydetergents and personal care body washes to impart residualantimicrobial activity to fabrics and hair and skin surfaces. Variousother water-insoluble or sparingly soluble particulate materials such assunscreen agents, fabric softeners, fabric brighteners, fabricwhiteners, etc., have also been employed in detergent compositions.Their activity depends on particle deposition and retention on washedsubstrates (skin, hair, fabrics, etc.). By its very nature an effectivedetergent composition tends to minimize retention of particulate matteron washed surfaces. Consequently, only a relatively small portion of theactive agents present in detergent compositions is actually retainedafter washing and rinsing of the substrate surface. Since the activityof the active agent depends on the quantity of the particles depositedand retained on the surface, a means to enhance active agent depositionand retention are highly desirable. The cationic cassia derivatives ofthe present invention are suitable for such purposes.

In styling shampoo, the use of the cationic cassia derivatives of thepresent invention as deposition aids to enhance the deposition ofwater-insoluble styling polymers improves the styling performance(conditioning, curl retention, superior hair feel) of the hair. Thecationic cassia derivatives of the invention can be used as depositionaids in combination with water-insoluble hair styling polymers selectedfrom the group of (meth)acrylates copolymers and silicone-grafted(meth)acrylates. Examples include t-butylacrylate/2-ethylhexylacrylatecopolymers, t-butylacrylate/2-ethylhexylmethacrylate copolymers, t-butylacrylate/2-ethylhexyl methacrylate/polydimethylsiloxane macromer, andt-butyl methacrylate/2-ethylhexylmethacrylate/polydimethylsiloxanemacromer copolymers, and mixtures thereof.

As previously discussed, various water-insoluble or sparingly solubleparticulate materials such as sunscreens, fabric softeners, fabricbrighteners, fabric whiteners, biocides, etc. are employed in cleaningcompositions. Their activity will depend on the particle deposition andretention on washed systems. By its very nature, an effective detergentcomposition tends to minimize retention of particulate matters on washedsurfaces. Thus, only a relatively small portion of the agents present insuch detergent composition is actually retained after washing andrinsing of the surface. Since the activity of the functional agentdepends on the quantity of the particles deposited and retained on thesurface, means to enhance deposition are highly desirable. Cationiccassia derivatives can be used as a deposition aid for those particulatematerials: for instance for depositing fabric softener on fabricsurfaces during laundering process, or depositing biocides on hardsurfaces during sanitization. For example, the use of cationic cassiaderivatives along with regular laundry detergents ingredients such assurfactants, builders, etc., shows improvement in softening propertiesdue to better deposition of the fabric softener on the surface andsignificantly more storage stability. From about 0.05 to about 5 wt. %of the overall composition is used for the cationic cassia derivativesas deposition aid. In one aspect of the invention when employed in acomposition that includes a surfactant, the ratio of cationic cassia tosurfactant can range from about 10:1 to about 1:10 (wt. to wt. basis).

Cationic cassia derivatives can also be used as a soil release agent inlaundry detergent composition. During the laundering operation, thesepolymers absorb onto the surface of the fabric immersed in the washsolution. The absorbed polymer forms a hydrophilic layer which remainson the fabric after it is removed from the wash solution and dried,thereby imparting soil release properties to the laundering fabric. Lowlevels of cationic cassia derivatives (0.3 to 5 wt. %) in combinationwith typical fabric softeners can provide the soil release propertieswithout adversely affecting the whiteness of fabric upon repeated usage.

1. A cosmeceutical composition comprising: a) a polygalactomannanpolymer having repeating units containing a D-mannosyl to D-galactosylresidue ratio of 5 to 1 wherein a portion of the hydrogen groups on thependant hydroxy substituents on the mannosyl and galactosyl residues aresubstituted with a group represented by the formula:—AR¹ wherein A is a substituted or unsubstituted alkylene groupcontaining 1 to 6 carbon atoms, and R¹ is a group independently selectedfrom —N(R³)₃ ⁺X⁻, —S(R³)₂ ⁺X⁻, and —P(R³)₃ ⁺X⁻, wherein R³ independentlyrepresents substituted and unsubstituted C₁ to C₂₄ alkyl, substitutedand unsubstituted benzyl and substituted and unsubstituted phenyl; and Xis any suitable anion that balances the charge on the onium cation; andb) an active ingredient selected from anti-aging agents, anti-cellulite,and anti-acne agents.
 2. A cosmeceutical composition of claim 1 whereinsaid alkyl, alkylene, phenyl and benzyl groups are substitutedmono-substituted or independently multi-substituted with a groupselected from C₁ to C₃ alkyl, hydroxyl, and halogen.
 3. A cosmeceuticalcomposition of claim 1 wherein X is a halide.
 4. A cosmeceuticalcomposition of claim 1 wherein at least one C-6 hydroxyl hydrogen issubstituted by the —AR¹ substituent.
 5. A cosmeceutical composition ofclaim 1 wherein said polygalactomannan repeating unit is represented bythe formula:

wherein R independently represents hydrogen, and —AR¹, wherein —AR¹ isdefined as above.
 6. A cosmeceutical composition of claim 5, wherein nrepresents an integer ranging from about 15 to about
 35. 7. Acosmeceutical composition of claim 1, wherein said active ingredient isselected from alpha-hydroxy acid and salts thereof, beta-hydroxy acid,alpha-amino acid, alpha-keto acid, and mixtures thereof.
 8. Acosmeceutical composition of claim 1, wherein said alpha-hydroxy acid isselected from lactic acid, glycolic acid, fruit acids, malic acid,citric acid, tartaric acid, 2-hydroxyoctanoic acid, glyceric acid,tartronic acid, gluconic acid, mandelic acid, benzilic acid, azelaicacid, acetic acid, alpha-lopioc acid, salicylic acid,alpha-hydroxybutyric acid, alpha-hydroxyisobutyric acid,alpha-hydroxyisocaproic acid, alpha-hydroxyisovaleric acid, atrolacticacid, arginine glycolate, ainmonium lactate, and sodium lactate.
 9. Acosmeceutical composition of claim 1, wherein said beta-hydroxy acid isselected from 3-hydroxy propanoic acid, beta-hydroxybutyric acid,beta-phenyl lactic acid, and beta-phenylpyruvic acid.
 10. Acosmeceutical composition of claim 1, wherein said alpha-amino acid isselected from aspartic acid, glutamic acid, and mixtures thereof.
 11. Acosmeceutical composition of claim 1, wherein said alpha-keto acid isselected from pyruvic acid.
 12. A cosmeceutical composition of claim 1,wherein said active ingredient is selected from retinoic acid,halocarboxylic acid, an acidic antioxidant, mineral acid, phytic acid,lysophosphatidic acid, and 5-octanoylsalicylic acid.
 13. A cosmeceuticalcomposition of claim 12, wherein said halocarboxylic acid istrichloroacetic acid.
 14. A cosmneceutical composition of claim 12,wherein said acidic antioxidant is ascorbic acid